A 13C-NMR study of non-planar distortions in amides

The technique of 13C-NMR spectroscopy of oriented systems to problems of biological importance has been suggested and used to investigate non-planar distortions in substituted amides—models for peptides. The studies in conjunction with the proton magnetic resonance data on 5N-[13C]methyl[13C]formamide oriented in a nematic solvent provide all the direct dipolar couplings between the interacting nuclei in the system. When the 13C- and the 1H-NMR experiments are performed under non-identical conditions, 22 different direct dipolar couplings are obtained. It is demostrated that they can be used to determine unambiguously non-planar distortions around the nitrogen atom together with other geometrical data and the molecular order.

Adsorption Of Methanol On The Surfaces Of Copper-Alloys - Ups And Eels Studies

Methanol adsorbs molecularly on the surfaces of Cu–Pd alloys at low temperatures and transforms to CH3O or CO on warming, depending upon the alloy composition. On oxygen presorbed Cu–Pd alloy surfaces, adsorption of methanol gives rise to H2O and H2CO. CH3OH adsorbed molecularly on the surfaces of Cu–Au alloys and CH3O is formed only at relatively high temperatures.

Gaussian-Maxwell beams

Gaussian-beam-type solutions to the Maxwell equations are constructed by using results from relativistic front analysis, and the propagation characteristics of these beams are analyzed. The rays of geometrical optics are shown to be the trajectories of energy flow, as given by the Poynting vector. The longitudinal components of the field vectors in the direction of the beam axis, though small, are shown to be essential for a consistent description.

Anisotropic Gaussian Schell-model beams: Passage through optical systems and associated invariants

Anisotropic Gaussian Schell-model (AGSM) fields and their transformation by first-order optical systems (FOS’s) forming Sp(4,R) are studied using the generalized pencils of rays. The fact that Sp(4,R), rather than the larger group SL(4,R), is the relevant group is emphasized. A convenient geometrical picture wherein AGSM fields and FOS’s are represented, respectively, by antisymmetric second-rank tensors and de Sitter transformations in a (3+2)-dimensional space is developed. These fields are shown to separate into two qualitatively different families of orbits and the invariants over each orbit, two in number, are worked out. We also develop another geometrical picture in a (2+1)-dimensional Minkowski space suitable for the description of the action of axially symmetric FOS’s on AGSM fields, and the invariants, now seven in number, are derived. Interesting limiting cases forming coherent and quasihomogeneous fields are analyzed.

Glass-Transition In Isopentane - A Monte-Carlo Study

Monte Carlo simulations with realistic interaction potentials have been carried out on isopentane to investigate the glass transition. Intermolecular pair-correlation functions of the glass show distinct differences from those of the liquid, the CH-CH pair-correlation function being uniquely different from the other pair-correlation functions. The coordination number of the glass is higher than that of the liquid, and the packing in the glass seems to be mainly governed by the geometrical constraints of the molecule. Annealing affects the properties of the glass significantly.

Reinvestigation of the structure of Feist's acid 3-methylene-trans-1,2-cyclopropanedicarboxylic acid

C6H604, Mr = 142, triclinic, P[, a = 4.842(1), b = 7.607(1), c = 9.168 (3) A, ~ = 98.41(2), fl = 99.89(2), y = 77.74(1) ° , V = 320.9/k 3, Z = 2, Dm= 1.45 (flotation), D x = 1.470 g cm -3, p(Mo Ktt, 2 = 0.7107 A) = 0.63 cm -~, F(000) = 148. The structure was solved by direct methods and refined to an R value of 0.038 for 723 intensity measurements. The geometrical changes in the cyclopropane ring are discussed in the light of substituent effects. In the crystal structure the carboxylic groups are disordered.

Analyzing multiple spike trains with nonparametric granger causality

Simultaneous recordings of spike trains from multiple single neurons are becoming commonplace. Understanding the interaction patterns among these spike trains remains a key research area. A question of interest is the evaluation of information flow between neurons through the analysis of whether one spike train exerts causal influence on another. For continuous-valued time series data, Granger causality has proven an effective method for this purpose. However, the basis for Granger causality estimation is autoregressive data modeling, which is not directly applicable to spike trains. Various filtering options distort the properties of spike trains as point processes. Here we propose a new nonparametric approach to estimate Granger causality directly from the Fourier transforms of spike train data. We validate the method on synthetic spike trains generated by model networks of neurons with known connectivity patterns and then apply it to neurons limultaneously recorded from the thalamus and the primary somatosensory cortex of a squirrel monkey undergoing tactile stimulation.

Structure of a new crystal form of 2- ([3-(trifluoromethyl)phenyl] amino)benzoic acid (flufenamic acid)

C14Ht0F3NO2, P2.Jc, a = 12.523 (4), b = 7.868(6), c = 12.874 (3)A, fl = 95.2 (2) ° , O,,, = 1.47 (4), D e = 1.47 Mg m -3, Z = 4. Final R = 0.074 for 2255 observed reflections. The carboxyl group and the phenyl ring bearing the carboxyl group are nearly coplanar whereas the two phenyl rings are inclined with respect to each other at 52.8 ° . The difference between the two polymorphs of flufenamic acid lies in the geometrical disposition of the [3-(trifluoromethyl)- phenyl]amino moiety with respect to the benzoic acid moiety. As in other fenamate structures, the carboxyl group and the imino N atom are connected through an intramolecular hydrogen bond; also, pairs of centrosymmetrically related molecules are connected through hydrogen bonds involving carboxyl groups.

A new method for generation of quasi-periodic structures withn fold axes: Application to five and seven folds

A new geometrical method for generating aperiodic lattices forn-fold non-crystallographic axes is described. The method is based on the self-similarity principle. It makes use of the principles of gnomons to divide the basic triangle of a regular polygon of 2n sides to appropriate isosceles triangles and to generate a minimum set of rhombi required to fill that polygon. The method is applicable to anyn-fold noncrystallographic axis. It is first shown how these regular polygons can be obtained and how these can be used to generate aperiodic structures. In particular, the application of this method to the cases of five-fold and seven-fold axes is discussed. The present method indicates that the recursion rule used by others earlier is a restricted one and that several aperiodic lattices with five fold symmetry could be generated. It is also shown how a limited array of approximately square cells with large dimensions could be detected in a quasi lattice and these are compared with the unit cell dimensions of MnAl6 suggested by Pauling. In addition, the recursion rule for sub-dividing the three basic rhombi of seven-fold structure was obtained and the aperiodic lattice thus generated is also shown.

A study on the nature of the compound layer formed during the ion nitriding of En40B steel

Commercial-grade En40B steel has been ion nitrided in the temperature range 475–550°C in a 25%N2–75%H2 gas mixture. The nature of the compound layer formed was studied by the X-ray diffraction technique and optical metallography. It was observed that the structure of the compound layer gradually transforms from a predominantly epsilon (Porson) nitride to a predominantly γ′ nitride structure with increasing treatment time. Optical metallography studies on sections orthogonal to the nitrided surface showed that, after about 5 h of treatment, the thickness of the compound layer decreases with further increase in treatment time.

On the Transform Method of Solution of an External Crack Problem

The breakdown of the usual method of Fourier transforms in the problem of an external line crack in a thin infinite elastic plate is discovered and the correct solution of this problem is derived using the concept of a generalised Fourier transform of a type discussed first by Golecki [1] in connection with Flamant's problem.

Solvent effects on the structure of N-methylpyrrole as studied by nmr in nematic solvents

The proton NMR spectra of N-methylpyrrole oriented in the nematic phases of liquid crystals with positive and negative diamagnetic anisotropies and their mixtures are reported. Geometrical parameters derived from the spectra at the critical point in the mixture of liquid crystals with positive and negative diamagnetic anisotropies, where macroscopic diamagnetic anisotropy vanishes, are similar to those obtained in the solvent with negative diamagnetic anisotropy. However, significant distortions in the molecular structure attributed to solvent effects have been observed in liquid crystals with positive diamagnetic anisotropy. The minimum energy conformation has one C---H of the methyl perpendicular to the ring.

Competing tetragonal and monoclinic phases in Ni2.2Mn0.80Ga

Temperature dependent synchrotron x-ray powder diffraction, differential scanning calorimetry, and magnetic measurements were performed on Ni2+xMn1-xGa (x=0.20 and 0.35) magnetic shape memory alloys. For x=0.20, though the monoclinic phase is thermodynamically stable, a trace of residual stress can stabilize a tetragonal phase. The residual-stress-induced tetragonal phase transforms to the cubic austenite phase over an unusually large temperature range (348 K < T < 693 K), suggesting extremely slow kinetics of transformation. In contrast to x=0.20, the thermodynamically stable phase of x=0.35 is tetragonal and this composition exhibits the usual features of a reversible martensitic transformation. The results suggest that for x=0.20 the monoclinic and tetragonal phases are nearly degenerate.

X-Ray Studies On Crystalline Complexes Involving Amino-Acids And Peptides .11. Peptide Aggregation And Water-Structure In The Crystals Of A Hydrated 1-1 Complex Between L-Histidyl-L-Serine And Glycyl-L-Glutamic Acid

The hexahydrate of a 1:1 complex between L-histidyl-L-serine and glycyl-L-glutamic acid crystallizes in space group P1 with a = 4.706(1), b= 8.578(2), c= 16.521(3) ÅA; α= 85.9(1), β= 89.7(1)°, = 77.4(1). The crystal structure, solved by direct methods, has been refined to an R value of 0.046 for 2150 observed reflections. The two peptide molecules in the structure have somewhat extended conformations. The unlike molecules aggregate into separate alternating layers. Each layer is stabilized by hydrogen bonded head-to-tail sequences as well as sequences of hydrogen bonds involving peptide groups. The arrangement of molecules in each layer is similar to one of the plausible idealized arrangements of L-alanyl-L-alanine worked out from simple geometrical considerations. Adjacent layers in the structure are held together by interactions involving side chains as well as water molecules. The water structure observed in the complex provides a good model, at atomic resolution, for that in protein crystals. An interesting feature of the crystal structure is the existence of two water channels in the interfaces between adjacent peptide layers.

Photochemical Reactions in Oriented Systems

Modification of chemical reactions through the use of constrained and/or organized media has attracted a great deal of attention recently. Results from our laboratory in this direction which include a study of photochemical reactions in solid state and in cyclodextrins are presented here. A study of solid state photochemical behavior of coumarins has provided information regarding subtler aspects of topochemical postulates of photodimerization. Results pertaining to geometrical criteria for photodimerization and "chloro" as a crystal engineering group are discussed. As a part of an attempt to correlate chemical reactivity with molecular packing in the solid state, photooxidation of diarylthioketones in the solid state has been investigated. The observed differences in the reactivity of these crystals are rationalized in terms of crystal packing. Though cyclodextrins have been extensively studied, very few photochemical reactions involving molecules complexed to cyclodextrins have been examined. In this connection, the utility of cyclodextrins in bringing about selectivity in photochemical reactions through the study of excited state behavior of olefins and aryl alkyl ketones has been demonstrated in our laboratory.